EP2655493B1 - Process for making enviromental friendly plasticizers - Google Patents

Process for making enviromental friendly plasticizers Download PDF

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Publication number
EP2655493B1
EP2655493B1 EP11784471.2A EP11784471A EP2655493B1 EP 2655493 B1 EP2655493 B1 EP 2655493B1 EP 11784471 A EP11784471 A EP 11784471A EP 2655493 B1 EP2655493 B1 EP 2655493B1
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Prior art keywords
process according
molecular
polymer material
polymer
rubber
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EP11784471.2A
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German (de)
French (fr)
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EP2655493A1 (en
Inventor
Carla Recker
Ewgeni HAAS
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Continental Reifen Deutschland GmbH
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Continental Reifen Deutschland GmbH
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/22—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by depolymerisation to the original monomer, e.g. dicyclopentadiene to cyclopentadiene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/12—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by dry-heat treatment only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
    • B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2317/00—Characterised by the use of reclaimed rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2319/00—Characterised by the use of rubbers not provided for in groups C08J2307/00 - C08J2317/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the invention relates to a process for the production of environmentally friendly plasticizer, which is particularly suitable for use in vehicle tires or technical rubber articles.
  • plasticizers form another important class of additives in rubber compounds, such as vehicle tires (pneumatic vehicle tires, two-wheel tires, solid rubber tires) and technical rubber articles (hoses, belts, straps, blankets, membranes, seals, air springs, bellows, automotive interior trim, artificial leather ) be used.
  • Plasticizers are sometimes added in large quantities to rubber blends to lower the blending price, improve the flow properties of the blend (energy savings in processing, avoid energy spikes), improve filler dispersion, improve make and bond performance and physical properties to influence the mixture and the vulcanizates prepared therefrom.
  • solid biomasses are the starting material for the preparation of the plasticizers, which in turn can take place via various types.
  • a method is based on the catalytic direct liquefaction, in which the pyrolysis takes place in an oil sump with catalyst addition.
  • Direct liquefaction processes are very general, for example in DE 102 15 679 A1 and DE 10 2005 040 490 A1 described.
  • a method for the direct liquefaction of biomass is known from Willner, Market Fruit Report 2005, Communications of the Chamber of Agriculture, Chamber of Agriculture Schleswig-Holstein, Kiel.
  • the problem here is that the available biomass is limited. If BTL production, both for fuels and for processing oils, is therefore used on a larger scale in the future, this will lead to competition for land and use due to the increased use of agricultural and forestry land. Similarly, the effort for harvesting, transport, shredding and other must be considered.
  • the invention is based on the object to provide a process for the production of environmentally friendly plasticizers, by which a plasticizer is obtained, which can ensure independence from petroleum as a source of raw material and energy source and on the other hand, the above problems, which BTL oils prepare, do not have. Furthermore, the starting materials for the production of the plasticizer should be relatively easily available.
  • This object is achieved by a process for the preparation of plasticizer, which is characterized in that high molecular weight vulcanized polymer material is converted by thermal direct liquefaction in a low molecular weight phase.
  • an environmentally friendly plasticizer can be prepared from polymer material.
  • the high molecular weight vulcanized polymer material is converted by thermal direct liquefaction in a low molecular weight phase.
  • the low molecular weight phase is recovered by a suitable route known to those skilled in the art and can be used as an environmentally friendly plasticizer for rubber compounds. This ultimately leads to a significant improvement in the life cycle assessment of end products, such as vehicle tires and technical rubber products.
  • Being present as a low molecular weight phase means that the plasticizer is present as a processing oil.
  • the high molecular weight vulcanized polymeric material is preferably rubbers, ie, elastic polymers, rubber blends (green or vulcanized), thermoplastic elastomers (TPE), blends containing TPE (green or vulcanized), thermoplastic or thermosetting plastics.
  • rubber compounds intended for use in tires or technical rubber articles (green mixture), intended (vulcanized mixture, waste) or already used for this purpose (vulcanized mixture, waste) can be used for the production of the plasticizer. Mixtures of two or more of the above polymer materials are possible. Since the polymer materials mentioned are usually waste materials, which z.Bsp.
  • TRG technical rubber goods
  • TRG technical rubber goods
  • the plasticizer produced by thermal direct liquefaction of polymer material may be used like a plasticizer heretofore used in the rubber industry.
  • There is a real “recycling” instead of “downcycling” because in the finished end products no compromises have to be made regarding the physical properties.
  • Known pyrolytic processes lead to plasticizers, which are used in the energetic utilization as fuel and whereby fillers contained in the rubber mixture lose their amplification potential significantly.
  • the polymer material is present in the form of polymer powder and / or polymer granules.
  • the polymer powder and / or the polymer granules are preferably based on used tires and in a preferred embodiment contain natural or synthetic rubber and / or butadiene rubber and / or styrene-butadiene rubber. These diene rubbers are commonly used for the production of tires and TRG and are therefore found in the corresponding waste materials.
  • a particularly good yield of plasticizer can be achieved in the presence of said rubbers in the polymer material. Preferably, yields of 90% or more are apparent.
  • the thermal direct liquefaction of polymer material takes place essentially in accordance with the BTL production. Particularly good results are achieved when the thermal direct liquefaction of polymer material at temperatures between 100 and 500 ° C, preferably at temperatures between 150 and 420 ° C, takes place.
  • the cracked bottoms phase may, in a preferred embodiment, be the final product.
  • the skilled person refers to the cleavage of hydrocarbons of longer chain length (high molecular weight) in hydrocarbons shorter chain length (low molecular weight, also referred to as low molecular weight).
  • At least one initial oil is used to convert the high molecular weight vulcanized polymer material into a low molecular weight phase. This applies both to the batch process and to the continuous process, wherein in the continuous process the stock oil is used essentially to start the process.
  • a master oil it is heated to a temperature suitable for the corresponding oil, and then the polymer material to be cracked is added.
  • a suitable temperature for the makeup oil should usually be a temperature at which the makeup oil does not yet completely decompose, as evidenced by the absence of a reactive current.
  • the original oil is selected from the group consisting of mineral oil, lubricants of long and geradkettenigen hydrocarbons vegetable oils and liquid polymer having an average molecular weight M w of 150 to 5000 g / mol.
  • the original oil is a BTL oil or an oil which has been prepared by the process according to the invention, or a mixture of these oils and / or the oils mentioned above.
  • Vegetable oils are mixtures of different acylglycerols and further contain other impurities, such as free fatty acids, phospholipids, dyes, sterols, essential oils, vitamins, etc.
  • the vegetable oils are rapeseed oil and / or sunflower oil.
  • mineral oil this is preferably selected from the group consisting of DAE (Distilled Aromatic Extracts) and / or RAE (Residual Aromatic Extract) and / or TDAE (Treated Distilled Aromatic Extracts) and / or MES (Mild Extracted Solvents) and or naphthenic oils, with TDAE being particularly preferred.
  • Table 1 shows the characterizations of the polymer materials used and of the plasticizer prepared by the process according to the invention.
  • the polymer material used is a rubber powder obtained from a vulcanized truck tread compound.
  • the rubber powder contains as rubber components high levels of a natural polyisoprene (NR), low levels of polybutadiene rubber (BR) and some traces of styrene butadiene rubber (SBR).
  • NR natural polyisoprene
  • BR polybutadiene rubber
  • SBR styrene butadiene rubber
  • the term phr (parts per hundred parts of rubber by weight) used in Table 1 is the quantity specification for mixture formulations customary in the rubber industry.
  • the dosage of the parts by weight of the individual substances is always based on 100 parts by weight of the total mass of all the rubbers present in the mixture.
  • the embodiment relates to experiments on a laboratory scale, for industrial applications are the appropriate parameters adapt, in particular depending on the corresponding reactor size.
  • the process oil was produced by the process according to the invention.
  • TDAE oil As a reference oil TDAE oil was used. 302.42 g of TDAE oil (VIVATEC 500, Hansen-Rosenthal KG, Hamburg) were heated to 300 ° C. in a reaction apparatus of 11 volumes. The warm-up period is 80 minutes to reach the desired bottom temperature of 300 ° C. Subsequently, this is held for 22 minutes to detect the so-called blank value.
  • the blank value is a product mass flow caused by the cracking of the feed oil. This stream is also present later on the addition of the polymeric material so that the total condensate mass flow during the experiment is composed of the blank and the mass flow caused by the addition of the polymer material. After the preheating time, the supply of the polymer material is started.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
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Description

Die Erfindung betrifft ein Verfahren zur Herstellung von umweltfreundlichem Weichmacher, welcher insbesondere zur Verwendung in Fahrzeugreifen oder technischen Gummiartikeln geeignet ist.The invention relates to a process for the production of environmentally friendly plasticizer, which is particularly suitable for use in vehicle tires or technical rubber articles.

Neben Kautschuk und Füllstoffen bilden die Weichmacher eine andere wichtige Klasse von Zuschlagstoffen in Kautschukmischungen, wie sie für Fahrzeugreifen (Fahrzeugluftreifen, Zweiradreifen, Vollgummireifen) und technischen Gummiartikeln (Schläuche, Riemen, Gurte, Drucktücher, Membranen, Dichtungen, Luftfedern, Bälge, Automobilinnenverkleidungen, Kunstleder) verwendet werden. Weichmacher werden Kautschukmischungen zum Teil in großen Mengen zugesetzt, um dem Mischungspreis zu senken, die Fließeigenschaften der Mischung zu verbessern (Energieeinsparung bei der Verarbeitung, Vermeidung von Energiespitzen), die Füllstoffdispersion zu verbessern, das Konfektionier- und das Klebverhalten zu verbessern und die physikalischen Eigenschaften der Mischung und der daraus hergestellten Vulkanisate zu beeinflussen.In addition to rubber and fillers, the plasticizers form another important class of additives in rubber compounds, such as vehicle tires (pneumatic vehicle tires, two-wheel tires, solid rubber tires) and technical rubber articles (hoses, belts, straps, blankets, membranes, seals, air springs, bellows, automotive interior trim, artificial leather ) be used. Plasticizers are sometimes added in large quantities to rubber blends to lower the blending price, improve the flow properties of the blend (energy savings in processing, avoid energy spikes), improve filler dispersion, improve make and bond performance and physical properties to influence the mixture and the vulcanizates prepared therefrom.

In der Regel ist die Basis fast aller in der Kautschukindustrie verwendeten Weichmacher Erdöl. Aus ökologischen Gesichtspunkten, vor allem im Bezug auf die gegebenen Schadstoffemissionen und Rohstoffknappheiten, ist Erdöl zukünftig als Ausgangsstoff für die Herstellung von Kautschuk-Weichmachern nicht mehr tragbar. Als Alternative werden beispielsweise Pflanzenöle als Weichmacher in Kautschukmischungen verwendet, wie beispielsweise in DE 101 08 981 A1 und DE 602 18 446 T2 beschrieben. Die dort beschriebenen Pflanzenöle können als alleiniger Weichmacher eingesetzt werden, meist werden sie aber in Kombination mit einem weiteren, aus Erdöl gewonnenen, Weichmacher verwendet. Aber auch die Pflanzenöle stehen allerdings nicht in beliebigen Mengen für die Kautschukindustrie zur Verfügung.
Als weitere Alternative wird in WO 2010/012531 A1 die Verwendung von sogenannten BTL-Ölen (Biomass-To-Liquid-Ölen) beschrieben. Hierbei sind feste Biomassen Ausgangstoff für die Herstellung der Weichmacher, die wiederum über verschiedene Arten erfolgen kann. Zu erwähnen sind hier beispielhaft die Flash-Pyrolyse, mit sehr kurzen Verweilzeiten im Reaktor, die hydrierende Direktverflüssigung, wo durch (Druck-) Wasserstoff während der Pyrolyse stabile Produktkohlenwasserstoffe entstehen, das so genannte Carbo-V-Verfahren, welches an das Fischer-Tropsch-Verfahren angelehnt ist und die katalytische Direktverflüssigung, bei der die Pyrolyse in einem Ölsumpf mit Katalysatorbeimengung erfolgt. Verfahren zur Direktverflüssigung sind sehr allgemein beispielsweise in DE 102 15 679 A1 und DE 10 2005 040 490 A1 beschrieben.
Ein Verfahren zur Direktverflüssigung von Biomassen ist aus Willner, Marktfruchtreport 2005, Mitteilungen der Landwirtschaftskammer, Landwirtschaftskammer Schleswig-Holstein, Kiel, bekannt.
Das Problem hierbei ist allerdings, dass die verfügbare Biomasse begrenzt ist. Wird die BTL-Herstellung, sowohl für Kraftstoffe als auch für Weichmacheröle, daher zukünftig in größerem Maßstab eingesetzt, so führt dies zu einer Flächen- und Nutzungskonkurrenz bedingt durch die erhöhte Nutzung von landwirtschaftlichen und forstwirtschaftlichen Flächen. Ebenso ist der Aufwand für Ernte, Transport, Schreddern und anderes zu berücksichtigen.As a rule, the basis of almost all softeners used in the rubber industry is petroleum. From an ecological point of view, above all with regard to the given pollutant emissions and scarcity of raw materials, petroleum is no longer sustainable as a raw material for the production of rubber plasticizers. As an alternative, for example, vegetable oils are used as plasticizers in rubber compounds, such as in DE 101 08 981 A1 and DE 602 18 446 T2 described. The vegetable oils described therein can be used as the sole plasticizer, but usually they are in combination with another, derived from petroleum, plasticizer used. However, the vegetable oils are not available in any quantities for the rubber industry.
As another alternative is in WO 2010/012531 A1 the use of so-called BTL oils (biomass-to-liquid oils) described. In this case, solid biomasses are the starting material for the preparation of the plasticizers, which in turn can take place via various types. Mention should be made here, by way of example, of flash pyrolysis, with very short residence times in the reactor, hydrogenating direct liquefaction, where (product) hydrocarbons are formed by (pressurized) hydrogen during pyrolysis, the so-called Carbo-V process, which is fed to the Fischer-Tropsch A method is based on the catalytic direct liquefaction, in which the pyrolysis takes place in an oil sump with catalyst addition. Direct liquefaction processes are very general, for example in DE 102 15 679 A1 and DE 10 2005 040 490 A1 described.
A method for the direct liquefaction of biomass is known from Willner, Market Fruit Report 2005, Communications of the Chamber of Agriculture, Chamber of Agriculture Schleswig-Holstein, Kiel.
The problem here, however, is that the available biomass is limited. If BTL production, both for fuels and for processing oils, is therefore used on a larger scale in the future, this will lead to competition for land and use due to the increased use of agricultural and forestry land. Similarly, the effort for harvesting, transport, shredding and other must be considered.

Der Erfindung liegt nun die Aufgabe zu Grunde, ein Verfahren zur Herstellung von umweltfreundlichen Weichmachern bereitzustellen, durch den ein Weichmacher erhalten wird, der zum Einen eine Unabhängigkeit gegenüber Erdöl als Rohstoffquelle und Energiequelle gewährleisten kann und zum Anderen die oben genannten Probleme, welche BTL-Öle bereiten, nicht aufweist. Des Weiteren sollen die Ausgangsstoffe für die Herstellung des Weichmachers relativ einfach verfügbar sein.The invention is based on the object to provide a process for the production of environmentally friendly plasticizers, by which a plasticizer is obtained, which can ensure independence from petroleum as a source of raw material and energy source and on the other hand, the above problems, which BTL oils prepare, do not have. Furthermore, the starting materials for the production of the plasticizer should be relatively easily available.

Gelöst wird diese Aufgabe durch ein Verfahren zur Herstellung von Weichmacher, welches dadurch gekennzeichnet ist, dass hochmolekulares vulkanisiertes Polymermaterial durch thermische Direktverflüssigung in eine niedrigmolekulare Phase umgewandelt wird.This object is achieved by a process for the preparation of plasticizer, which is characterized in that high molecular weight vulcanized polymer material is converted by thermal direct liquefaction in a low molecular weight phase.

Überraschenderweise wurde gefunden, dass sich ein umweltfreundlicher Weichmacher aus Polymermaterial herstellen lässt.
Hierzu wird das hochmolekulare vulkanisierte Polymermaterial durch thermische Direktverflüssigung in eine niedrigmolekulare Phase umgewandelt. Nach der Umwandlung wird die niedrigmolekulare Phase auf geeignetem und dem der fachkundigen Person bekannten Weg gewonnen und kann als umweltfreundlicher Weichmacher für Kautschukmischungen verwendet werden. Dies führt letztendlich zu einer deutlichen Verbesserung der Ökobilanz der Endprodukte, wie Fahrzeugreifen und technische Gummiartikel.
Das Vorliegen als niedrigmolekulare Phase bedeutet, dass der Weichmacher als Weichmacheröl vorliegt.
Bei dem hochmolekularen vulkanisierten Polymermaterial handelt es bevorzugt um Kautschuke, d.h. elastische Polymere, Kautschukmischungen (grün oder vulkanisiert), thermoplastische Elastomere (TPE), Mischungen, welche TPE enthalten (grün oder vulkanisiert), thermoplastische oder duroplastische Kunststoffe. Insbesondere Kautschukmischungen, welche zur Verwendung in Reifen oder technischen Gummiartikeln vorgesehen sind (grüne Mischung), vorgesehen waren (vulkanisierte Mischung, Abfälle) oder bereits hierfür verwendet wurden (vulkanisierte Mischung, Altabfälle) können zur Herstellung des Weichmachers eingesetzt werden. Gemische aus zwei oder mehr der oben genannten Polymermaterialien sind möglich.
Da es sich bei den genannten Polymermaterialien in der Regel um Abfallstoffe handelt, welche z.Bsp. während oder nach der Produktion von Reifen oder technischen Gummiartikeln (TRG = technical rubber goods) anfallen, welche als Altreifen oder Alt-TRGs vorliegen oder welche als Kunststoffabfälle bspw aus Verpackungen oder ähnlichem, bspw. Schredderleichtfraktionen, vorliegen, wird durch das erfindungsgemäße Verfahren ein zusätzlicher Verwertungsweg für derartige Abfallstoffe geschaffen.Surprisingly, it has been found that an environmentally friendly plasticizer can be prepared from polymer material.
For this purpose, the high molecular weight vulcanized polymer material is converted by thermal direct liquefaction in a low molecular weight phase. After conversion, the low molecular weight phase is recovered by a suitable route known to those skilled in the art and can be used as an environmentally friendly plasticizer for rubber compounds. This ultimately leads to a significant improvement in the life cycle assessment of end products, such as vehicle tires and technical rubber products.
Being present as a low molecular weight phase means that the plasticizer is present as a processing oil.
The high molecular weight vulcanized polymeric material is preferably rubbers, ie, elastic polymers, rubber blends (green or vulcanized), thermoplastic elastomers (TPE), blends containing TPE (green or vulcanized), thermoplastic or thermosetting plastics. In particular, rubber compounds intended for use in tires or technical rubber articles (green mixture), intended (vulcanized mixture, waste) or already used for this purpose (vulcanized mixture, waste) can be used for the production of the plasticizer. Mixtures of two or more of the above polymer materials are possible.
Since the polymer materials mentioned are usually waste materials, which z.Bsp. occur during or after the production of tires or technical rubber goods (TRG = technical rubber goods), which are available as used tires or old TRGs or as plastic waste, for example, from packaging or the like, for example. Schredderleichtfraktionen, are present by the inventive method an additional Recycling path for such waste created.

Der durch thermische Direktverflüssigung von Polymermaterial hergestellte Weichmacher kann wie ein bisher in der Kautschukindustrie verwendeter Weichmacher eingesetzt werden. Es findet dabei ein echtes "Recycling" statt und kein "Downcycling", da in den fertigen Endprodukten keine Kompromisse hinsichtlich der physikalischen Eigenschaften eingegangen werden müssen.
Dies liegt insbesondere im Fall von füllstoffhaltigen Polymermaterialien auch daran, dass durch die Verwendung der thermischen Direktverflüssigung von Polymermaterial der so hergestellte Weichmacher keinen negativen Einfluss auf die Verstärkungswirkung der üblicherweise in Kautschukmischungen enthaltenen Füllstoffe hat. Bekannte pyrolytische Verfahren führen zu Weichmachern, die in der energetischen Verwertung als Brennstoff eingesetzt werden und wodurch in der Kautschukmischung enthaltene Füllstoffe ihr Verstärkungspotential deutlich verlieren.The plasticizer produced by thermal direct liquefaction of polymer material may be used like a plasticizer heretofore used in the rubber industry. There is a real "recycling" instead of "downcycling" because in the finished end products no compromises have to be made regarding the physical properties.
In particular, in the case of filler-containing polymer materials, this is also due to the fact that the use of the thermal direct liquefaction of polymer material does not have a negative effect on the reinforcing effect of the fillers usually contained in rubber mixtures. Known pyrolytic processes lead to plasticizers, which are used in the energetic utilization as fuel and whereby fillers contained in the rubber mixture lose their amplification potential significantly.

Im Hinblick auf eine vereinfachte Prozessführung hat es sich als vorteilhaft gezeigt, wenn das Polymermaterial in Form von Polymerpulver und / oder Polymergranulat vorliegt. Dies führt zu einer vereinfachten Zuführung des Polymermaterials in die entsprechende Reaktionsapparatur.
Das Polymerpulver und / oder das Polymergranulat ist bevorzugt auf der Basis von Altreifen und enthält in einer bevorzugten Ausführungsform natürlichen oder synthetischen Kautschuk und / oder Butadienkautschuk und / oder Styrolbutadienkautschuk.
Diese Dienkautschuke werden üblicherweise zur Herstellung von Reifen und TRG verwendet und sind daher in den entsprechenden Abfallstoffen zu finden. Des Weiteren lässt sich bei Vorhandensein von den genannten Kautschuken im Polymermaterial eine besonders gute Ausbeute an Weichmacher erzielen. Bevorzugt zeigen sich Ausbeuten von 90% oder mehr.
Die thermische Direktverflüssigung von Polymermaterial findet im Wesentlichen in Anlehnung an die BTL-Herstellung statt.
Besonders gute Ergebnisse werden erzielt, wenn die thermische Direktverflüssigung von Polymermaterial bei Temperaturen zwischen 100 und 500°C, bevorzugt bei Temperaturen zwischen 150 und 420°C, stattfindet.With regard to a simplified process management, it has proven to be advantageous if the polymer material is present in the form of polymer powder and / or polymer granules. This leads to a simplified supply of the polymer material in the corresponding reaction apparatus.
The polymer powder and / or the polymer granules are preferably based on used tires and in a preferred embodiment contain natural or synthetic rubber and / or butadiene rubber and / or styrene-butadiene rubber.
These diene rubbers are commonly used for the production of tires and TRG and are therefore found in the corresponding waste materials. Furthermore, a particularly good yield of plasticizer can be achieved in the presence of said rubbers in the polymer material. Preferably, yields of 90% or more are apparent.
The thermal direct liquefaction of polymer material takes place essentially in accordance with the BTL production.
Particularly good results are achieved when the thermal direct liquefaction of polymer material at temperatures between 100 and 500 ° C, preferably at temperatures between 150 and 420 ° C, takes place.

Vorteilhaft ist es ebenso, wenn das hochmolekulare vulkanisierte Polymermaterial in einer Sumpfphase gecrackt wird.
Die gecrackte Sumpfphase kann in einer bevorzugten Ausführungsform das Endprodukt darstellen.
Als Cracken bezeichnet die fachkundige Person die Spaltung von Kohlenwasserstoffen längerer Kettenlänge (hochmolekular) in Kohlenwasserstoffe kürzerer Kettenlänge (niedermolekular, auch als niedrigmolekular bezeichnet).It is also advantageous if the high molecular weight vulcanized polymer material is cracked in a sump phase.
The cracked bottoms phase may, in a preferred embodiment, be the final product.
As cracking, the skilled person refers to the cleavage of hydrocarbons of longer chain length (high molecular weight) in hydrocarbons shorter chain length (low molecular weight, also referred to as low molecular weight).

Bei der BTL-Herstellung wird oft in einstufige und zweistufige Verfahren unterschieden, wobei bei zweistufigen Verfahren im Herstellungsprozess im Wesentlichen in einem ersten Verfahrensschritt die Erzeugung eines Synthesegases mittels Vergasung und in einem zweiten Verfahrensschritt die Synthetisierung eines Treibstoffes erfolgt.
Im Rahmen des erfindungsgemäßen Verfahrens hat es sich als vorteilhaft gezeigt, wenn das Cracken einstufig stattfindet. Das einstufige Verfahren liefert eine gute Ausbeute und spart gleichzeitig einen weiteren Verfahrensschritt ein.
Des Weiteren kann das Verfahren absatzweise, d.h. schrittweise, oder kontinuierlich durchgeführt werden, wobei letztere die besonders bevorzugte Variante ist, da sie im industriellen Maßstab am wenigsten aufwendig ist.In BTL production, a distinction is often made in single-stage and two-stage processes, wherein in two-stage processes in the production process substantially in a first process step, the production of a synthesis gas by gasification and in a second process step, the synthesis of a fuel.
In the context of the method according to the invention, it has proven to be advantageous if the cracking takes place in one stage. The one-step process provides a good yield and at the same time saves a further process step.
Furthermore, the process can be carried out batchwise, ie stepwise, or continuously, the latter being the particularly preferred variant, since it is the least expensive on an industrial scale.

Ebenso hat es sich als vorteilhaft gezeigt, wenn zur Umwandlung des hochmolekularen vulkanisierten Polymermaterials in eine niedrigmolekulare Phase wenigstens ein Vorlageöl verwendet wird. Dies gilt sowohl für das absatzweise Verfahren als auch für das kontinuierliche Verfahren, wobei beim kontinuierlichen Verfahren das Vorlageöl im Wesentlichen zum Anfahren des Prozesses verwendet wird.
Zunächst wird bei Verwendung eines Vorlageöls selbiges auf eine für das entsprechende Öl geeignete Temperatur erwärmt und anschließend wird das zu crackende Polymermaterial hinzugefügt. Eine geeignete Temperatur für das Vorlageöl sollte in der Regel eine Temperatur sein, bei der sich das Vorlageöl noch nicht vollständig anfängt zu zersetzen, was durch das Nicht-Vorhandensein eines Blindstroms zeigt.Likewise, it has been shown to be advantageous if at least one initial oil is used to convert the high molecular weight vulcanized polymer material into a low molecular weight phase. This applies both to the batch process and to the continuous process, wherein in the continuous process the stock oil is used essentially to start the process.
First, when using a master oil, it is heated to a temperature suitable for the corresponding oil, and then the polymer material to be cracked is added. A suitable temperature for the makeup oil should usually be a temperature at which the makeup oil does not yet completely decompose, as evidenced by the absence of a reactive current.

In einer bevorzugten Ausführungsform ist das Vorlageöl ausgewählt ist aus der Gruppe bestehend aus Mineralöl, Schmiermitteln aus langen und geradketteigen Kohlenwasserstoffen Pflanzenölen und flüssigem Polymer mit einem mittleren Molekulargewicht Mw von 150 bis 5000 g/mol. Es ist aber auch möglich, dass das Vorlageöl ein BTL-Öl oder ein Öl ist, welches nach dem erfindungsgemäßen Verfahren hergestellt wurde, oder ein Gemisch diesen Ölen und / oder den oben genannten Ölen.In a preferred embodiment, the original oil is selected from the group consisting of mineral oil, lubricants of long and geradkettenigen hydrocarbons vegetable oils and liquid polymer having an average molecular weight M w of 150 to 5000 g / mol. But it is also possible that the original oil is a BTL oil or an oil which has been prepared by the process according to the invention, or a mixture of these oils and / or the oils mentioned above.

Pflanzenöle sind Gemische unterschiedlicher Acylglycerolen und enthalten weiterhin noch weitere Begleitstoffe, wie freie Fettsäuren, Phospholipide, Farbstoffe, Sterole, ätherische Öle, Vitamine, etc. In einer bevorzugten Ausführungsform handelt es sich bei den Pflanzenölen um Rapsöl und / oder um Sonnenblumenöl.Vegetable oils are mixtures of different acylglycerols and further contain other impurities, such as free fatty acids, phospholipids, dyes, sterols, essential oils, vitamins, etc. In a preferred embodiment, the vegetable oils are rapeseed oil and / or sunflower oil.

Bei der Verwendung von Mineralöl ist dieses bevorzugt ausgewählt aus der Gruppe, bestehend aus DAE (Destillated Aromatic Extracts) und / oder RAE (Residual Aromatic Extract) und / oder TDAE (Treated Destillated Aromatic Extracts) und / oder MES (Mild Extracted Solvents) und / oder naphtenische Öle, wobei TDAE besonders bevorzugt ist.When using mineral oil, this is preferably selected from the group consisting of DAE (Distilled Aromatic Extracts) and / or RAE (Residual Aromatic Extract) and / or TDAE (Treated Distilled Aromatic Extracts) and / or MES (Mild Extracted Solvents) and or naphthenic oils, with TDAE being particularly preferred.

Die Erfindung soll nun anhand eines Ausführungsbeispiels näher erläutert werden. Hierzu sind in Tabelle 1 die Charakterisierungen der verwendeten Polymermaterialien und des anhand des erfindungsgemäßen Verfahrens hergestellten Weichmachers aufgeführt.The invention will now be explained in more detail with reference to an embodiment. Table 1 shows the characterizations of the polymer materials used and of the plasticizer prepared by the process according to the invention.

Ausführungsbeispielembodiment

Als Polymermaterial wird ein Gummipulver verwendet, welches aus einer vulkanisierten LKW-Laufstreifenmischung gewonnen wurde. Das Gummipulver enthält als Kautschukkomponenten hohe Anteile eines natürlichen Polyisoprens (NR), geringe Anteile von Polybutadienkautschuk (BR) und z.T. nur Spuren von Styrolbutadienkautschuk (SBR). Die in der Tabelle 1 verwendete Angabe phr (parts per hundred parts of rubber by weight) ist dabei die in der Kautschukindustrie übliche Mengenangabe für Mischungsrezepturen. Die Dosierung der Gewichtsteile der einzelnen Substanzen wird dabei stets auf 100 Gewichtsteile der gesamten Masse aller in der Mischung vorhandenen Kautschuke bezogen. Das Ausführungsbeispiel bezieht sich auf Versuche im Labormaßstab, für industrielle Anwendungen sind die entsprechenden Parameter anzupassen, insbesondere in Abhängigkeit von der entsprechenden Reaktorgröße.
Das Weichmacheröl wurde nach dem erfindungsgemäßen Verfahren hergestellt. Als Vorlageöl wurde TDAE-Öl verwendet. In einer Reaktionsapparatur von 11 Volumen wurden 302,42g TDAE-Öl (VIVATEC 500, Hansen-Rosenthal KG, Hamburg) auf 300°C erwärmt. Die Aufwärmphase beträgt 80 Minuten, um die gewünschte Sumpftemperatur von 300°C zu erreichen. Anschließend wird diese 22 Minuten gehalten, um den sogenannten Blindwert zu erfassen. Der Blindwert ist ein Produktmassenstrom, der durch das Cracken des Vorlageöles verursacht wird. Dieser Strom ist auch später bei der Zugabe des Polymermaterials vorhanden, so dass sich der gesamte Kondensatmassenstrom während des Versuches aus dem Blindwert und dem Massenstrom, der durch die Zugabe des Polymermaterials verursacht wird, zusammensetzt. Nach Ablauf der Vorwärmzeit wird die Zufuhr des Polymermaterials gestartet. Dabei ist noch zu beachten, einen Fraktionswechsel vorzunehmen, um den Einfluss des Polymermaterials auf das entstandene Kondensat besser auswerten zu können. Während der kontrollierten und kontinuierlichen Zufuhr des Polymermaterials wird das Drehmoment des Rührers in der Reaktionsapparatur beobachtet werden, um sicherzustellen, dass die Viskosität des Sumpfes nicht zu stark ansteigt. Bei temporären Viskositätsanstiegen kann kontrolliert eine kurze Pause bei der Zufuhr des Polymermaterials vorgenommen werden. Es werden im vorliegenden Ausführungsbeispiel 604,31g Polymermaterial mit einer Geschwindigkeit von 111,57 g/h in einem Zeitraum von 325 Minuten hinzugefügt. Die Temperatur während der gesamten thermischen Direktverflüssigung wird bei 300°C gehalten.
Tabelle 1 zeigt, dass keine Anteile an hochmolekularem Polymermaterial mehr vorhanden sind.The polymer material used is a rubber powder obtained from a vulcanized truck tread compound. The rubber powder contains as rubber components high levels of a natural polyisoprene (NR), low levels of polybutadiene rubber (BR) and some traces of styrene butadiene rubber (SBR). The term phr (parts per hundred parts of rubber by weight) used in Table 1 is the quantity specification for mixture formulations customary in the rubber industry. The dosage of the parts by weight of the individual substances is always based on 100 parts by weight of the total mass of all the rubbers present in the mixture. The embodiment relates to experiments on a laboratory scale, for industrial applications are the appropriate parameters adapt, in particular depending on the corresponding reactor size.
The process oil was produced by the process according to the invention. As a reference oil TDAE oil was used. 302.42 g of TDAE oil (VIVATEC 500, Hansen-Rosenthal KG, Hamburg) were heated to 300 ° C. in a reaction apparatus of 11 volumes. The warm-up period is 80 minutes to reach the desired bottom temperature of 300 ° C. Subsequently, this is held for 22 minutes to detect the so-called blank value. The blank value is a product mass flow caused by the cracking of the feed oil. This stream is also present later on the addition of the polymeric material so that the total condensate mass flow during the experiment is composed of the blank and the mass flow caused by the addition of the polymer material. After the preheating time, the supply of the polymer material is started. It should also be noted to make a fraction change in order to better evaluate the influence of the polymer material on the resulting condensate can. During the controlled and continuous delivery of the polymeric material, the torque of the stirrer will be observed in the reaction apparatus to ensure that the viscosity of the sump does not increase too much. With temporary increases in viscosity, a short break in the supply of the polymer material can be controlled. In the present embodiment, 604.31 g of polymer material are added at a rate of 111.57 g / h over a period of 325 minutes. The temperature throughout the thermal direct liquefaction is maintained at 300 ° C.
Table 1 shows that no higher molecular weight polymer material is present.

Folgende Prüfmethoden wurden verwendet, sofern nicht direkt in der Tabelle angegeben:

  • Aceton-Extrakt (= Summe aller aus der vulkanisierten Gummimischung extrahierbaren Substanzen, wie bspw. Alterungsschutzmittel, Weichmacher, etc) gemäß DIN DIN ISO 308
  • Rußgehalt mit TGA gemäß DIN 51006
  • Glührückstand bei 550°C gemäß DIN 53568, DIN 12904, DIN 12491
  • Schwefelgehalt gemäß ASTM D2622
  • Glasübergangstemperatur Tg gemäß ISO DIS 28343
  • Gehalt an polycyclischen Aromaten (PAK-Wert) gemäß IP 346
  • Stickstoffgehalt in Anlehnung an ASTM 147
  • Zn-, Cu-, Fe-Gehalt in Anlehnung an ASTM D7260
Tabelle 1 Prüfmethode Einheit Pulver 1 Weichmacheröl Aceton Extrakt % 6,4 -- Rußgehalt Gew.-% 28,7 15,2 Glührückstand % 6 3,2 Schwefelgehalt % 1,22 1,11 Tg °C -62 -17 NR phr 83 -- BR phr 17 -- SBR phr Spuren -- PAK % -- 0,12 Stickstoffgehalt % -- 0,23 Zn % 1,06 0,58 Cu mg/kg 1,4 3,5 Fe mg/kg 24,9 7,6 Viskosität @ RT n. a. pastös The following test methods were used, unless indicated directly in the table:
  • Acetone extract (= sum of all extractable from the vulcanized rubber compound substances, such as. Anti-aging agents, plasticizers, etc) according to DIN DIN ISO 308th
  • Carbon black content with TGA according to DIN 51006
  • Glue residue at 550 ° C according to DIN 53568, DIN 12904, DIN 12491
  • Sulfur content according to ASTM D2622
  • Glass transition temperature Tg according to ISO DIS 28343
  • Polycyclic aromatic content (PAK value) according to IP 346
  • Nitrogen content based on ASTM 147
  • Zn, Cu, Fe content in accordance with ASTM D7260
<b> Table 1 </ b> Test method unit Powder 1 processing oil Acetone extract % 6.4 - carbon black content Wt .-% 28.7 15.2 Residue on ignition % 6 3.2 sulfur content % 1.22 1.11 Tg ° C -62 -17 NO phr 83 - BR phr 17 - SBR phr traces - PAK % - 0.12 nitrogen content % - 0.23 Zn % 1.06 0.58 Cu mg / kg 1.4 3.5 Fe mg / kg 24.9 7.6 Viscosity @ RT n / A pasty

Claims (10)

  1. Process for producing plasticizer, characterized in that high-molecular-weight vulcanized polymer material is converted to a low-molecular-weight phase via direct thermal liquefaction.
  2. Process according to Claim 1, characterized in that the high-molecular-weight vulcanized polymer material takes the form of polymer powder and/or granulated polymer.
  3. Rubber mixture according to Claim 2, characterized in that it is the polymer powder and/or the granulated polymer based on used tires.
  4. Process according to Claim 2 or 3, characterized in that the polymer powder and/or the granulated polymer comprises natural or synthetic rubber and/or butadiene rubber and/or styrene-butadiene rubber.
  5. Process according to any of Claims 1 to 4, characterized in that the direct thermal liquefaction takes place at temperatures of from 100 to 500°C.
  6. Process according to Claim 5, characterized in that the direct thermal liquefaction takes place at temperatures of from 150 to 420°C.
  7. Process according to any of Claims 1 to 6, characterized in that the high-molecular-weight vulcanized polymer material in a bottom phase is cracked.
  8. Process according to any of Claims 1 to 7, characterized in that the high-molecular-weight vulcanized polymer material is cracked in a single stage.
  9. Process according to any of Claims 1 to 8, characterized in that for the conversion of the high-molecular-weight vulcanized polymer material to a low-molecular-weight phase at least one feed oil is used.
  10. Process according to Claim 9, characterized in that the feed oil is one selected from the group consisting of mineral oil, lubricants made of long and short-chain hydrocarbons, vegetable oils and liquid polymer with an average molar mass Mw of from 150 to 5000 g/mol.
EP11784471.2A 2010-12-22 2011-11-11 Process for making enviromental friendly plasticizers Active EP2655493B1 (en)

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PCT/EP2011/069925 WO2012084335A1 (en) 2010-12-22 2011-11-11 Method for producing environmentally-friendly plasticisers

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US10179479B2 (en) 2015-05-19 2019-01-15 Bridgestone Americas Tire Operations, Llc Plant oil-containing rubber compositions, tread thereof and race tires containing the tread

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FR2472000A1 (en) * 1979-12-20 1981-06-26 Rhone Poulenc Ind PROCESS FOR IMPROVING COMPATIBILITY OF PLASTIFIERS AND LOADS IN POLYMERS
DE3704118A1 (en) * 1986-05-17 1987-11-19 Huels Chemische Werke Ag FOAMABLE, GELLABLE AND HEAT-CURABLE MASS FOR THE PRODUCTION OF LATEX FOAM
US5364996A (en) * 1992-06-09 1994-11-15 Texaco Inc. Partial oxidation of scrap rubber tires and used motor oil
US5836524A (en) * 1996-10-01 1998-11-17 National Science Council Liquefaction of wastes with product oil recycling
DE10108981A1 (en) 2001-02-23 2002-09-12 Continental Ag Rubber compound for tire treads
DE60218446T2 (en) 2001-03-12 2007-11-29 Société de Technologie Michelin RUBBER COMPOSITION FOR TIRES
DE10215679B4 (en) 2002-04-10 2007-07-12 Ibh Ingenieurgesellschaft Mbh Direct thermochemical conversion of high molecular weight organic substances into low viscosity liquid fuels
PL201443B3 (en) * 2002-10-18 2009-04-30 Alexei Matveev Method of processing of organic industrial and municipal wastes containing rubber
RU2220986C1 (en) * 2003-04-24 2004-01-10 Общество с ограниченной ответственностью "Н.Т.Д Таманно" Method of processing rubber-containing wastes
DE102005040490A1 (en) 2005-07-25 2007-02-08 Demir, Yaver Apparatus and Process for a Biofuel Refinery: Direct thermochemical conversion of organic substances to liquid fuels
US20080072478A1 (en) * 2006-09-22 2008-03-27 Barry Cooper Liquefaction Process
DE102008037714A1 (en) 2008-07-31 2010-02-04 Continental Reifen Deutschland Gmbh Rubber compound with environmentally friendly plasticizer

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